US6262286B1 - Method for selective production of racemic metallocene complexes - Google Patents

Method for selective production of racemic metallocene complexes Download PDF

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US6262286B1
US6262286B1 US09/508,970 US50897000A US6262286B1 US 6262286 B1 US6262286 B1 US 6262286B1 US 50897000 A US50897000 A US 50897000A US 6262286 B1 US6262286 B1 US 6262286B1
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Heike Gregorius
Carsten Süling
Wolfgang Bidell
Hans-Herbert Brintzinger
Hans-Robert-Hellmuth Damrau
Armin Weber
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S526/943—Polymerization with metallocene catalysts

Definitions

  • the present invention relates to a process for preparing racemic metallocene complexes by reacting bridged or unbridged aromatic transition metal complexes of the formula I
  • M is titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten or an element of transition group III of the Periodic Table and the lanthanides,
  • X are identical or different and are each fluorine, chlorine, bromine, iodine, hydrogen C 1 -C 10 -alkyl, C 6 -C 15 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, —OR 10 or —NR 10 R 11 ,
  • n is an integer from 1 to 4, where n corresponds to the valence of M minus 2,
  • R 1 , R 8 are identical or different and are each fluorine, chlorine, bromine, iodine, C 1 -C 20 -alkyl, 3- to 8-membered cycloalkyl which in turn may bear a C 1 -C 10 -alkyl group as substituent, C 6 -C 15 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, Si(R 9 ) 3 where R 9 are identical or different and are each C 1 -C 20 -alkyl, C 3 -C 10 -cycloalkyl, C 6 -C 15 -aryl, where the radicals mentioned may be partially or fully substituted by heteroatoms,
  • R 10 , R 11 are C 1 -C 10 -alkyl, C 6 -C 15 -aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical,
  • Y, Y 1 are identical or different and are each
  • ⁇ BR 12 ⁇ AlR 12 , —Ge—, —Sn—, —O—, —S—, ⁇ SO, ⁇ SO 2 , ⁇ NR 12 , ⁇ CO, ⁇ PR 12 or ⁇ P(O)R 12 ,
  • R 12 are identical or different and are each hydrogen, halogen, C 1 -C 10 -alkyl, C 1 -C 10 -fluoroalkyl, C 6 -C 10 -fluoroaryl, C 6 -C 10 -aryl, C 1 -C 10 -alkoxy, C 2 -C 10 -alkenyl, C 7 -C 40 -arylalkyl, C 8 -C 40 -arylalkenyl, C 7 -C 40 -alkylaryl, or two radicals R 12 together with the atoms connecting them form a ring,
  • M 1 is silicon, germanium or tin and
  • n 0, 1, 2 or 3
  • Y is non-bridging and is two radicals R′ and R′′, where
  • R′ and R′′ are identical or different and are each hydrogen, fluorine, chlorine, bromine, iodine, C 1 -C 20 -alkyl, 3- to 8-membered cycloalkyl which in turn may bear a C 1 -C 10 -alkyl radical as substituent, C 6 -C 15 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, Si(R 9 ) 3 where R 9 are identical or different and are each C 1 -C 20 -alkyl, C 3 -C 10 -cycloalkyl, C 6 -C 15 -aryl, or together with adjacent radicals R 4 or R 5 form saturated, partially saturated or unsaturated cyclic groups having from 4 to 15 carbon atoms, and the radicals mentioned can
  • M is titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten or an element of transition group III of the Periodic Table and of the lanthanides,
  • R 1 , R 8 are identical or different and are each fluorine, chlorine, bromine, iodine, C 1 -C 20 -alkyl, 3- to 8-membered cycloalkyl which may in turn bear a C 1 -C 10 -alkyl group as substituent, C 6 -C 15 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, Si(R 9 ) 3 where R 9 are identical or different and are each C 1 -C 20 -alkyl, C 3 -C 10 -cycloalkyl, C 6 -C 15 -aryl, where the radicals mentioned may be partially or fully substituted by heteroatoms,
  • R 2 to R 7 are identical or different and are each hydrogen, C 1 -C 20 -alkyl, 3- to 8-membered cycloalkyl which may in turn bear a C 1 -C 10 -alkyl radical as substituent, C 6 -C 15 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, Si(R 9 ) 3 where R 9 are identical or different and are each C 1 -C 20 -alkyl, C 3 -C 10 -cycloalkyl, C 6 -C 15 -aryl, and adjacent radicals R 2 to R 7 may form saturated, partially saturated or unsaturated cyclic groups having from 4 to 15 carbon atoms and the radicals mentioned may be fully or partially substituted by heteroatoms,
  • Y, Y 1 are identical or different and are each
  • ⁇ BR 12 ⁇ AlR 12 , —Ge—, —Sn—, —O—, —S—, ⁇ SO, ⁇ SO 2 , ⁇ NR 12 , ⁇ CO, ⁇ PR 12 or ⁇ P(O)R 12 ,
  • R 12 are identical or different and are each hydrogen, halogen, C 1 -C 10 -alkyl, C 1 -C 10 -fluoroalkyl, C 6 -C 10 -fluoroaryl, C 6 -C 10 -aryl, C 1 -C 10 -alkoxy, C 2 -C 10 -alkenyl, C 7 -C 40 -arylalkyl, C 8 -C 40 -arylalkenyl, C 7 -C 40 -alkylaryl, or two radicals R 12 together with the atoms connecting them form a ring,
  • M 1 is silicon, germanium or tin and
  • n 0, 1, 2 or 3
  • Y is non-bridging and is two radicals R′ and R′′, where
  • R′ and R′′ are identical or different and are each hydrogen, fluorine, chlorine, bromine, iodine, C 1 -C 20 -alkyl, 3- to 8-membered cycloalkyl which in turn may bear a C 1 -C 10 -alkyl radical as substituent, C 6 -C 15 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, Si(R 9 ) 3 where R 9 are identical or different and are each C 1 -C 20 -alkyl, C 3 -C 10 -cycloalkyl, C 6 -C 15 -aryl, or together with adjacent radicals R 4 or R 5 form saturated, partially saturated or unsaturated cyclic groups having from 4 to 15 carbon atoms, and the radicals mentioned can
  • R 13 to R 17 are identical or different and are each hydrogen, C 1 -C 20 -alkyl, 5- to 7-membered cycloalkyl which may in turn bear a C 1 -C 10 -alkyl group as substituent, C 6 -C 15 -aryl or arylalkyl, where adjacent radicals may together form cyclic groups having from 4 to 15 carbon atoms, or Si(R 18 ) 3 where
  • R 18 are identical or different and are each C 1 -C 10 -alkyl, C 6 -C 15 -aryl or C 3 -C 10 -cycloalkyl,
  • R 19 to R 23 are identical or different and are each hydrogen, C 1 -C 20 -alkyl, 5- to 7-membered cycloalkyl which may in turn bear a C 1 -C 10 -alkyl group as substituent, C 6 -C 15 -aryl or arylalkyl, where adjacent radicals may together form cyclic groups having from 4 to 15 carbon atoms, or Si(R 24 ) 3 where
  • R 24 are identical or different and are each C 1 -C 10 -alkyl, C 6 -C 15 -aryl or C 3 -C 10 -cycloalkyl,
  • R 16 and Z together form a group —[T(R 25 )(R 26 )] q —E—, where
  • T can be identical or different and are each silicon, germanium, tin or carbon,
  • R 25 , R 26 are each hydrogen, C 1 -C 10 -alkyl, C 3 -C 10 -cycloalkyl or C 6 -C 15 -aryl
  • q 1, 2, 3 or 4
  • R 27 are identical or different and are each C 1 -C 10 -alkyl, C 6 -C 15 -aryl, C 3 -C 10 -cycloalkyl, alkylaryl or Si(R 28 ) 3
  • R 28 are identical or different and are each C 1 -C 10 -alkyl, C 6 -C 15 -aryl, C 3 -C 10 -cycloalkyl or alkylaryl
  • racemic metallocene complexes of the formula III as catalysts or as constituents of catalysts for the polymerization of olefinically unsaturated compounds or as reagents or as catalysts in stereoselective synthesis.
  • enantioselective organic synthesis is increasingly providing interesting possibilities for using chiral metallocene complexes of metals of transition groups III-VI of the Periodic Table of the Elements.
  • enantioselective hydrogenations of prochiral substrates for example prochiral olefins as described in R. Waymouth, P. Pino, J. Am. Chem. Soc. 112 (1990), pp. 4911-4914, or prochiral ketones, imines and oximes as described in WO 92/9545.
  • a further object is to find racemic metallocene complexes which can either be used directly as or in catalysts, primarily for olefin polymerization, or which after modification, for example after substitution by an “auxiliary ligand”, can be used as or in catalysts, primarily for olefin polymerization, or which can be used as reagents or catalysts in stereoselective synthesis.
  • racemic metallocene complexes III and their use as catalysts or in catalysts for the polymerization of olefinically unsaturated compounds or as reagents or catalysts in stereoselective synthesis.
  • the term “virtualy meso-free” means that at least 90% of a compound is present in the form of the racemate.
  • bridged or unbridged aromatic transition metal complexes of the present invention have the formula I
  • M is titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten or an element of transition group III of the Periodic Table and the lanthanides,
  • X are identical or different and are each fluorine, chlorine, bromine, iodine, hydrogen C 1 -C 10 -alkyl, C 6 -C 15 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, —OR 10 or —NR 10 R 11 ,
  • n is an integer from 1 to 4, where n corresponds to the valence of M minus 2,
  • R 1 , R 8 are identical or different and are each fluorine, chlorine, bromine, iodine, C 1 -C 20 -alkyl, 3- to 8-membered cycloalkyl which in turn may bear a C 1 -C 10 -alkyl group as substituent, C 6 -C 15 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, Si(R 9 ) 3 where R 9 are identical or different and are each C 1 -C 20 -alkyl, C 3 -C 10 -cycloalkyl, C 6 -C 15 -aryl, where the radicals mentioned may be partially or fully substituted by heteroatoms,
  • R 2 to R 7 are identical or different and are each hydrogen, C 1 -C 20 -alkyl, 3- to 8-membered cycloalkyl which in turn may bear a C 1 -C 10 -alkyl radical as substituent, C 6 -C 15 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, Si(R 9 ) 3 where R 9 are identical or different and are each C 1 -C 20 -alkyl, C 3 -C 10 -cycloalkyl, C 6 -C 15 -aryl, and adjacent radicals R 2 to R 7 may form saturated, partially saturated or unsaturated cyclic groups having from 4 to 15 carbon atoms, and the radicals mentioned can be fully or partially substituted by heteroatoms,
  • R 10 , R 11 are C 1 -C 10 -alkyl, C 6 -C 15 -aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical,
  • Y, Y 1 are identical or different and are each
  • ⁇ BR 12 ⁇ AlR 12 , —Ge—, —Sn—, —O—, —S—, ⁇ SO, ⁇ SO 2 , ⁇ NR 12 , ⁇ CO, ⁇ PR 12 or ⁇ P(O)R 12 ,
  • R 12 are identical or different and are each hydrogen, halogen, C 1 -C 10 -alkyl, C 1 -C 10 -fluoroalkyl, C 6 -C 10 -fluoroaryl, C 6 -C 10 -aryl, C 1 -C 10 -alkoxy, C 2 -C 10 -alkenyl, C 7 -C 40 -arylalkyl, C 8 -C 40 -arylalkenyl, C 7 -C 40 -alkylaryl, or two radicals R 12 together with the atoms connecting them form a ring,
  • M 1 is silicon, germanium or tin and
  • n 0, 1, 2 or 3
  • Y is non-bridging and is two radicals R′ and R′′, where
  • R′ and R′′ are identical or different and are each hydrogen, fluorine, chlorine, bromine, iodine, C 1 -C 20 -alkyl, 3- to 8-membered cycloalkyl which in turn may bear a C 1 -C 10 -alkyl radical as substituent, C 6 -C 15 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, Si(R 9 ) 3 where R 9 are identical or different and are each C 1 -C 20 -alkyl, C 3 -C 10 -cycloalkyl, C 6 -C 15 -aryl, or together with adjacent radicals R 4 or R 5 form saturated, partially saturated or unsaturated cyclic groups having from 4 to 15 carbon atoms, and the radicals mentioned can
  • Preferred metals M are titanium, zirconium and hafnium, in particular zirconium.
  • substituents X are fluorine, chlorine, bromine, iodine, preferably chlorine, also C 1 -C 6 -alkyl such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, i-butyl or preferably tert-butyl.
  • substituents X are alkoxides —OR 10 or amides —NR 10 R 11 where R 10 or R 11 is C 1 -C 10 -alkyl, C 6 -C 15 -aryl, alkylaryl, arylalkyl, fluoroalkyl or fluoroaryl each having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical.
  • radicals X are, for example, methyl, ethyl, i-propyl, tert-butyl, phenyl, naphthyl, p-tolyl, benzyl, trifluoromethyl, pentafluorophenyl.
  • the substituents R 1 and R 8 are identical or different and are each fluorine, chlorine, bromine, iodine, C 1 -C 20 -alkyl, 3- to 8-membered cycloalkyl which may in turn bear a C 1 -C 10 -alkyl radical as substituent, e.g. methyl, ethyl or propyl.
  • Examples of such cycloalkyl radicals are cyclopropyl, cyclopentyl, preferably cyclohexyl, norbornyl.
  • the substituents R 1 and R 8 may also be C 6 -C 15 -aryl such as phenyl, naphthyl; alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, e.g. p-tolyl; arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, e.g.
  • benzyl or neophyl or they are triorganosilyl such as Si(R 9 ) 3 where R 9 are identical or different and are each C 1 -C 20 -alkyl, C 3 -C 10 -cycloalkyl, C 6 -C 15 -aryl, for example trimethylsilyl, tert-butyldimethylsilyl, triphenylsilyl.
  • the radicals mentioned can, of course, also be partially or fully substituted by heteroatoms, for example by S—, N—, O—, or halogen-containing structural elements. Examples of such substituted radicals R 1 and R 8 are trifluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, pentafluorophenyl.
  • Preferred substituents R 1 and R 8 are those which take up a lot of space. Such substituents are usually called bulky substituents. They are distinguished by the fact that they can cause steric hindrance.
  • these groups are organic or organosilicon radicals which take up a lot of space (bulky radicals), but also fluorine and preferably chlorine, bromine and iodine.
  • the number of carbon atoms in such organic or organosilicon radicals is usually not less than three.
  • Preferred non-aromatic, bulky radicals are those organic or organosilicon radicals which are branched in the ⁇ position or a higher position. Examples of such radicals are branched C 3 -C 20 -aliphatic, C 9 -C 20 -araliphatic and C 3 -C 10 -cycloaliphatic radicals, e.g.
  • radicals of this type are organosilicon radicals having from three to thirty carbon atoms, for example trimethylsilyl, triethylsilyl, triphenylsilyl, tert-butyldimethylsilyl, tritolylsilyl or bis(trimethylsilyl)methyl.
  • Preferred aromatic, bulky groups are, as a rule, C 6 -C 20 -aryl radicals such as phenyl, 1- or 2-naphthyl or preferably C 1 -C 10 -alkyl- or C 3 -C 10 -cycloalkyl-substituted aromatic radicals such as 2,6-dimethylphenyl, 2,6-di-tert-butylphenyl, mesityl.
  • C 6 -C 20 -aryl radicals such as phenyl, 1- or 2-naphthyl or preferably C 1 -C 10 -alkyl- or C 3 -C 10 -cycloalkyl-substituted aromatic radicals such as 2,6-dimethylphenyl, 2,6-di-tert-butylphenyl, mesityl.
  • R 1 and R 8 are i-propyl, tert-butyl, trimethylsilyl, cyclohexyl, i-butyl, trifluoromethyl, 3,5-dimethylphenyl.
  • R 1 and R 8 in formula I are identical.
  • the substituents R 2 to R 7 are identical or different and are each hydrogen, C 1 -C 20 -alkyl, 3- to 8-membered cycloalkyl which may in turn bear a C 1 -C 10 -alkyl radical such as methyl, ethyl or propyl as substituent.
  • Examples of such cycloalkyl radicals are cyclopropyl, cyclopentyl, preferably cyclohexyl, norbornyl.
  • substituents R 2 to R 7 may be C 6 -C 15 -aryl, such as phenyl or naphthyl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, e.g. p-tolyl, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, e.g.
  • benzyl or neophyl or they are triorganosilyl such as Si(R 9 ) 3 where R 9 are identical or different and are each C 1 -C 20 -alkyl, C 3 -C 10 -cycloalkyl or C 6 -C 15 -aryl, for example trimethylsilyl, tert-butyldimethylsilyl, triphenylsilyl.
  • the radicals R 2 to R 7 can also be connected to one another in such a way that adjacent radicals form saturated, partially saturated or unsaturated cyclic groups having from 4 to 15 carbon atoms.
  • the radicals R 3 and R 4 and/or the radicals R 5 and R 6 are connected via a C 2 -bridge in such a way that a benzo-fused ring system (naphthyl derivative) is formed.
  • the radicals R 2 to R 7 can, of course, also be partially or fully substituted by heteroatoms, for example by S—, N—, O—, or halogen-containing structural elements. Examples of such substituted radicals R 2 to R 7 are trifluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, pentafluorophenyl.
  • radicals R 2 and R 7 are identical and are each hydrogen and R 3 , R 4 , R 5 and R 6 are as defined above.
  • Suitable bridging units Y, Y 1 are the following:
  • ⁇ BR 12 ⁇ AlR 12 , —Ge—, —Sn—, —O—, —S—, ⁇ SO, ⁇ SO 2 , ⁇ NR 12 , ⁇ CO, ⁇ PR 12 or ⁇ P(O)R 12 ,
  • R 12 are identical or different and are each a hydrogen atom, a halogen atom, a C 1 -C 10 -alkyl group, a C 1 -C 10 -fluoroalkyl group, a C 6 -C 10 -fluoroaryl group, a C 6 -C 10 -aryl group, a C 1 -C 10 -alkoxy group, a C 2 -C 10 -alkenyl group, a C 7 -C 40 -arylalkyl group, a C 8 -C 40 -arylalkenyl group or a C 7 -C 40 -alkylaryl group or R 12 and R 13 or R 12 and R 14 , in each case together with the atoms connecting them, form a ring,
  • M 1 is silicon, germanium or tin.
  • Preferred bridging units Y, Y 1 are methylene —CH 2 —, S, O, —C(CH 3 )2—, where m in formula I is preferably 1 or 2; Y 1 are very particularly preferably identical and are each oxygen —O—. Very particular preference is given to phenoxide-type structures in which m in the formula I is zero, ie. the aromatic ring systems are linked directly to one another, for example to form a biphenyl derivative.
  • Y represent radicals R′ and R′′ which are identical or different and are fluorine, chlorine, bromide, iodine, C 1 -C 20 -alkyl or 3- to 8-membered cycloalkyl which may in turn bear a C 1 -C 10 -alkyl radical such as methyl, ethyl or propyl.
  • cycloalkyl radicals are cyclopropyl, cyclopentyl, preferably cyclohexyl, norbornyl.
  • substituents R′ and R′′ are C 6 -C 15 -aryl such as phenyl or naphthyl; alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, e.g. p-tolyl; arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, e.g.
  • benzyl or neophyl or triorganosilyl such as Si(R 9 ) 3 where R 9 are identical or different and are each C 1 -C 20 -alkyl, C 3 -C 10 -cycloalkyl or C 6 -C 15 -aryl, for example trimethylsilyl, tert-butyldimethylsilyl or triphenylsilyl.
  • the radicals mentioned can of course also be fully or partially substituted by heteroatoms, for example by structural elements containing S, N, O or halogen atoms.
  • R′ and R′′ are the trifluoromethyl, pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl and pentafluorophenyl groups.
  • R′ and R′′ are particularly preferably identical.
  • Very particularly preferred unbridged aromatic transition metal complexes are ones in which R 1 , R 8 , R′ and R′′ are identical.
  • bridged or unbridged aromatic transition metal complexes I are generally prepared by methods with which those skilled in the art are familiar.
  • the biphenol is first deprotonated in a solvent, for example tetrahydrofuran (THF), for example using sodium hydride or n-butyllithium, and the transition metal compound, for example the halide such as titanium tetrachloride, zirconium tetrachloride or hafnium tetrachloride, advantageously in the form of the bis-THF adducts, is subsequently added.
  • THF tetrahydrofuran
  • the transition metal compound for example the halide such as titanium tetrachloride, zirconium tetrachloride or hafnium tetrachloride, advantageously in the form of the bis-THF adducts.
  • the product is generally obtained by crystallization after removal of salts.
  • Unbridged transition metal phenoxide complexes can be prepared, for example, as described by H. Yasuda et al., J. Organomet. Chem.
  • the bridged or unbridged aromatic transition metal complexes I of the present invention generally still contain from 2 to 4 equivalents of a Lewis base which is generally introduced as a result of the synthetic route.
  • Lewis bases are ethers such as diethyl ether or tetrahydrofuran (THF). It is, however, also possible to obtain the aromatic transition metal complexes free of Lewis bases, for example by drying under reduced pressure or by selecting other solvents in the synthesis. Such measures are known to those skilled in the art.
  • the racemic metallocene complexes of the present invention are prepared by reacting the bridged or unbridged aromatic transition metal complexes I with cyclopentadienyl derivatives of the alkali metals or alkaline earth metals. Preference is given to using aromatic transition metal complexes I in which M is zirconium and the radicals R 1 and R 8 have the preferred meanings described above. Very useful aromatic transition metal complexes I are dichlorobis(6-tert-butyl-4-methylphenoxy)zirconium.(THF) 2 and the zirconium phenoxide compounds mentioned in the examples.
  • suitable cyclopentadienyl derivatives of the alkali metals or alkaline earth metals are those which, after reaction with the bridged aromatic transition metal complexes I of the present invention, selectively give virtually meso-free, racemic metallocene complexes.
  • the racemic metallocene complexes of the present invention may be bridged, but do not have to be.
  • a high barrier to rotation, in particular in the temperature range from 20 to 80° C., (which can be determined by 1 H and/or 13 C-NMR-spectroscopy) of the unbridged cyclopentadienyl-type ligands in the metallocene is sufficient to enable the metallocene complexes to be isolated directly in their racemic form without them being able to transform into the meso form.
  • the barrier to rotation necessary to ensure this is usually above 20 kJ/mol.
  • M 2 is Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba,
  • R 13 to R 17 are identical or different and are each hydrogen, C 1 -C 20 -alkyl, 5- to 7-membered cycloalkyl which may in turn bear a C 1 -C 10 -alkyl group as substituent, C 6 -C 15 -aryl or arylalkyl, where adjacent radicals may together form cyclic groups having from 4 to 15 carbon atoms, or Si(R 18 ) 3 where
  • R 18 are identical or different and are each C 1 -C 10 -alkyl, C 6 -C 15 -aryl or C 3 -C 10 -cycloalkyl,
  • R 19 to R 23 are identical or different and are each hydrogen, C 1 -C 20 -alkyl, 5- to 7-membered cycloalkyl which may in turn bear a C 1 -C 10 -alkyl group as substituent, C 6 -C 15 -aryl or arylalkyl, where adjacent radicals may together form cyclic groups having from 4 to 15 carbon atoms, or Si(R 24 ) 3 where
  • R 24 are identical or different and are each C 1 -C 10 -alkyl, C 6 -C 15 -aryl or C 3 -C 10 -cycloalkyl,
  • R 16 and Z together form a group —[T(R 25 )(R 26 )] n —E—
  • T can be identical or different and are each silicon, germanium, tin or carbon,
  • R 25 , R 26 are each hydrogen, C 1 -C 10 -alkyl, C 3 -C 10 -cycloalkyl or C 6 -C 15 -aryl
  • n 1, 2, 3 or 4
  • A is —O—
  • R 27 are identical or different and are each C 1 -C 10 -alkyl, C 6 -C 15 -aryl, C 3 -C 10 -cycloalkyl, alkylaryl or Si(R 28 ) 3
  • R 28 are identical or different and are each C 1 -C 10 -alkyl, C 6 -C 15 -aryl, C 3 -C 10 -cycloalkyl or alkylaryl,
  • Preferred compounds of the formula II are those in which M 2 is lithium, sodium and in particular magnesium. Furthermore, particular preference is given to those compounds of the formula II a)
  • R 17 and R 23 are substituents different from hydrogen, e.g. C 1 -C 10 -alkyl, such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, i-butyl or hexyl, also C 6 -C 10 -aryl, such as phenyl or trialkylsilyl, such as trimethylsilyl, T(R 25 R 26 ) is bis-C 1 -C 10 -alkylsilyl or bis-C 6 -C 10 -arylsilyl, e.g.
  • Very particularly preferred compounds II are those which are described in the examples and additionally
  • Such alkali metal or alkaline earth metal compounds II can be obtained by literature methods, for example by the, preferably stoichiometric, reaction of an organometallic compound or a hydride of the alkali or alkaline earth metal with the corresponding cyclopentadienyl-type hydrocarbons.
  • Suitable organometallic compounds are, for example, n-butyllithium or di-n-butylmagnesium.
  • the reaction of the bridged or unbridged aromatic transition metal complexes I with the cyclopentadienyl derivatives of alkali or alkaline earth metals, preferably of the formula II or IIa), is usually carried out in an organic solvent or suspension medium, preferably in an ether such as diethyl ether, THF and at from ⁇ 78 to 100° C., preferably at from 0 to 60° C.
  • the molar ratio of the aromatic transition metal complex I to the cyclopentadienyl derivative of alkali or alkaline earth metals is usually in the range from 0.8:1 to 1:1.2, preferably 1:1.
  • racemic metallocene complexes of the present invention are preferably those of the formula III
  • M is titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten or an element of transition group III of the Periodic Table and the lanthanides,
  • R 1 , R 8 are identical or different and are each fluorine, chlorine, bromine, iodine, C 1 -C 20 -alkyl, 3- to 8-membered cycloalkyl which may in turn bear a C 1 -C 10 -alkyl group as substituent, C 6 -C 15 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, Si(R 9 ) 3 where R 9 are identical or different and are each C 1 -C 20 -alkyl, C 3 -C 10 -cycloalkyl, C 6 -C 15 -aryl, where the radicals mentioned may be partially or fully substituted by heteroatoms,
  • R 2 to R 7 are identical or different and are each hydrogen, C 1 -C 20 -alkyl, 3- to 8-membered cycloalkyl which may in turn bear a C 1 -C 10 -alkyl radical as substituent, C 6 -C 15 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, Si(R 9 ) 3 where R 9 are identical or different and are each C 1 -C 20 -alkyl, C 3 -C 10 -cycloalkyl, C 6 -C 15 -aryl, and adjacent radicals R 2 to R 7 may form saturated, partially saturated or unsaturated cyclic groups having from 4 to 15 carbon atoms and the radicals mentioned may be fully or partially substituted by heteroatoms,
  • Y, Y 1 are identical or different and are each
  • ⁇ BR 12 ⁇ AlR 12 , —Ge—, —Sn—, —O—, —S—, ⁇ SO, ⁇ SO 2 , ⁇ NR 12 , ⁇ CO, ⁇ PR 12 or ⁇ P(O)R 12 ,
  • R 12 are identical or different and are each hydrogen, halogen, C 1 -C 10 -alkyl, C 1 -C 10 -fluoroalkyl, C 6 -C 10 -fluoroaryl, C 6 -C 10 -aryl, C 1 -C 10 -alkoxy, C 2 -C 10 -alkenyl, C 7 -C 40 -arylalkyl, C 8 -C 40 -arylalkenyl, C 7 -C 40 -alkylaryl, or two radicals R 12 together with the atoms connecting them form a ring,
  • M 1 is silicon, germanium or tin and
  • n 0, 1, 2 or 3
  • Y is non-bridging and is two radicals R′ and R′′, where
  • R′ and R′′ are identical or different and are each hydrogen, fluorine, chlorine, bromine, iodine, C 1 -C 20 -alkyl, 3- to 8-membered cycloalkyl which in turn may bear a C 1 -C 10 -alkyl radical as substituent, C 6 -C 15 -aryl, alkylaryl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, arylalkyl having from 1 to 10 carbon atoms in the alkyl radical and from 6 to 20 carbon atoms in the aryl radical, Si(R 9 ) 3 where R 9 are identical or different and are each C 1 -C 20 -alkyl, C 3 -C 10 -cycloalkyl, C 6 -C 15 -aryl, or together with adjacent radicals R 4 or R 5 form saturated, partially saturated or unsaturated cyclic groups having from 4 to 15 carbon atoms, and the radicals mentioned can
  • R 13 to R 17 are identical or different and are each hydrogen, C 1 -C 20 -alkyl, 5- to 7-membered cycloalkyl which may in turn bear a C 1 -C 10 -alkyl group as substituent, C 6 -C 15 -aryl or arylalkyl, where adjacent radicals may together form cyclic groups having from 4 to 15 carbon atoms, or Si(R 18 ) 3 where
  • R 18 are identical or different and are each C 1 -C 10 -alkyl, C 6 -C 15 -aryl or C 3 -C 10 -cycloalkyl,
  • R 19 to R 23 are identical or different and are each hydrogen, C 1 -C 20 -alkyl, 5- to 7-membered cycloalkyl which may in turn bear a C 1 -C 10 -alkyl group as substituent, C 6 -C 15 -aryl or arylalkyl, where adjacent radicals may together form cyclic groups having from 4 to 15 carbon atoms, or Si(R 24 ) 3 where
  • R 24 are identical or different and are each C 1 -C 10 -alkyl, C 6 -C 15 -aryl or C 3 -C 10 -cycloalkyl,
  • R 16 and Z together form a group —[T(R 25 )(R 26 )] q —E—, where
  • T can be identical or different and are each silicon, germanium, tin or carbon,
  • R 25 , R 26 are each hydrogen, C 1 -C 10 -alkyl, C 3 -C 10 -cycloalkyl or C 6 -C 15 -aryl
  • q 1, 2, 3 or 4
  • A is —O—
  • R 27 are identical or different and are each C 1 -C 10 -alkyl, C 6 -C 15 -aryl, C 3 -C 10 -cycloalkyl, alkylaryl or Si(R 28 ) 3
  • R 28 are identical or different and are each C 1 -C 10 -alkyl, C 6 -C 15 -aryl, C 3 -C 10 -cycloalkyl or alkylaryl.
  • Preferred compounds of the formula III are those in which M is titanium, hafnium or, in particular, zirconium. Furthermore, particular preference is given to bridged compounds of the formula III (ansa-metallocenes) in which R 17 and R 23 are substituents different from hydrogen, e.g.
  • C 1 -C 10 -alkyl such as methyl, ethyl, n-propyl, i-propyl, n-butyl, sec-butyl, tert-butyl, i-butyl, hexyl
  • C 6 -C 10 -aryl such as phenyl or trialkylsilyl, such as trimethylsilyl
  • T(R 25 R 26 ) is bis-C 1 -C 10 -alkylsilyl or bis-C 6 -C 10 -arylsilyl, e.g.
  • dimethylsilyl, diphenylsilyl, also 1,2-ethanediyl, methylene and the radicals R 13 to R 15 and R 19 to R 25 are as defined above and, in particular, form an indenyl-type ring system or a benzindenyl-type ring system.
  • Very particularly preferred compounds III are those which are described in the examples and additionally
  • racemic metallocene complexes preferably those of the formula III, can generally be modified further.
  • a bridged bisphenoxide ligand X 1 in the complex III can, for example, be split off (replaced) and reused.
  • organoaluminum compounds such as tri-C 1 -C 10 -alkylaluminum, e.g. trimethylaluminum, triethylaluminum, tri-n-butylaluminum or tri-iso-butylaluminum.
  • organoaluminum binaphthoxide an analogous method can also be employed if the ligand X 1 in the complex III consists of two unbridged phenoxide ligands.
  • the components are usually used in the stoichiometric ratio.
  • the stereochemistry of the metallocene complexes is generally retained during the cleavage reactions, ie. there is generally no conversion of the racemic form into the meso form of the metallocene complexes.
  • the process of the present invention makes it possible to obtain the racemic form of metallocene complexes very selectively.
  • Bridged indenyl- or benzindenyl-type metallocenes which have a ligand different from hydrogen in the vicinity of the bridging unit (the 2 position) can be obtained particularly advantageously.
  • racemic metallocene complexes of the present invention in particular those of the formula III or their above-described derivatives which can be obtained, for example, by replacement of the phenoxide ligands, can be used as catalysts or in catalyst systems for the polymerization of olefinically unsaturated compounds such as ethylene, propylene, 1-butene, 1-hexene, 1-octene or styrene.
  • olefinically unsaturated compounds such as ethylene, propylene, 1-butene, 1-hexene, 1-octene or styrene.
  • Their use is particularly advantageous in the stereoselective polymerization of prochiral, olefinically unsaturated compounds such as propylene and styrene.
  • Suitable catalysts or catalyst systems in which the racemic metallocene complexes of the present invention can function as “metallocene component” are usually obtained by means of compounds capable of forming metallocenium ions, as are described, for example, in EP-A-0 700 935, page 7, line 34 to page 8, line 21 and formulae (IV) and (V).
  • Further compounds capable of forming metallocenium ions are aluminoxanes (RAlO) n such as methylaluminoxane.
  • racemic metallocene complexes of the present invention in particular those of the formula III or their above-described derivatives which can be obtained, for example, by splitting off the phenoxide ligands, can also be used as reagents or as catalysts or in catalyst systems in stereoselective, in particular organic, synthesis.

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US20040010157A1 (en) * 2000-06-29 2004-01-15 Robert Damrau Method for the selective production of racemic metallocene complexes
WO2004037838A1 (en) * 2002-10-25 2004-05-06 Basell Polyolefine Gmbh Preparation of partially hydrogenated rac-ansa-metallocene complexes
US6914144B2 (en) 2002-01-29 2005-07-05 Merck & Co., Inc. Process for preparing integrin antagonist intermediate
US20060052587A1 (en) * 2002-10-25 2006-03-09 Basell Polyolefine Gmbh Racemoselective preparation of isolable ansa-metallocene biphenoxide complexes
US20060111527A1 (en) * 2002-10-25 2006-05-25 Hans-Robert-Hellmuth Damrau Racemoselective preparation of bridged metallocene complexes having unsubstituted or 2-substituted indenyl ligands
US20060167295A1 (en) * 2002-10-25 2006-07-27 Hans-Robert Damrau Racemoselective synthesis of rac-diorganosilylbis(2-methylbenzo[e]indeyl)zirconium componds
US20100204466A1 (en) * 2005-12-14 2010-08-12 Abbott Laboratories One pot synthesis of tetrazole derivatives of rapamycin
US20100274035A1 (en) * 2005-12-20 2010-10-28 Mueller Patrik Process for Recycling Cyclopentadienyl Derivatives and Preparing Metallocenes From Recycled, Substituted Cyclopentadienyl Derivatives
US12319772B2 (en) 2019-09-25 2025-06-03 Borealis Ag Catalysts

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DE10200422A1 (de) * 2002-01-08 2003-07-17 Basell Polyolefine Gmbh Verfahren zur Herstellung von Dialkyl-ansa-Metallocenen
EA015044B1 (ru) * 2006-02-08 2011-04-29 Сауди Бейсик Индастриз Корпорейшн Способ олигомеризации этилена
KR101278336B1 (ko) 2007-10-25 2013-06-25 루머스 노보렌 테크놀로지 게엠베하 안사-메탈로센 화합물의 라세모선택적 합성, 안사-메탈로센 화합물, 이를 포함하는 촉매, 그 촉매를 이용한 올레핀 폴리머 제조 공정, 그리고 올레핀 호모- 및 코폴리머
WO2025051400A1 (en) 2023-09-07 2025-03-13 Borealis Ag Methods of producing metallocene catalyst components

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US6992204B2 (en) 2000-06-29 2006-01-31 Basell Polyolefine Gmbh Method for the selective production of racemic metallocene complexes
US20040010157A1 (en) * 2000-06-29 2004-01-15 Robert Damrau Method for the selective production of racemic metallocene complexes
US6914144B2 (en) 2002-01-29 2005-07-05 Merck & Co., Inc. Process for preparing integrin antagonist intermediate
US7193099B2 (en) 2002-10-25 2007-03-20 Basell Polyolefine Gmbh Racemoselective preparation of isolable ansa-metallocene biphenoxide complexes
US20080200708A1 (en) * 2002-10-25 2008-08-21 Basell Polyolefine Gmbh Preparation of Partially Hydrogenated Rac-Ansa-Metallocene Complexes
US20060111527A1 (en) * 2002-10-25 2006-05-25 Hans-Robert-Hellmuth Damrau Racemoselective preparation of bridged metallocene complexes having unsubstituted or 2-substituted indenyl ligands
US20060167295A1 (en) * 2002-10-25 2006-07-27 Hans-Robert Damrau Racemoselective synthesis of rac-diorganosilylbis(2-methylbenzo[e]indeyl)zirconium componds
US7098354B2 (en) 2002-10-25 2006-08-29 Basell Polyolefine Gmbh Racemoselective synthesis of rac-diorganosilylbis(2-methylbenzo[e]indeyl)zirconium compounds
WO2004037838A1 (en) * 2002-10-25 2004-05-06 Basell Polyolefine Gmbh Preparation of partially hydrogenated rac-ansa-metallocene complexes
US7358381B2 (en) 2002-10-25 2008-04-15 Basell Polyolefine Gmbh Racemoselective preparation of bridged metallocene complexes having unsubstituted or 2-substituted indenyl ligands
US20060052587A1 (en) * 2002-10-25 2006-03-09 Basell Polyolefine Gmbh Racemoselective preparation of isolable ansa-metallocene biphenoxide complexes
US7619106B2 (en) * 2002-10-25 2009-11-17 Basell Polyolefine Gmbh Preparation of partially hydrogenated rac-ansa-metallocene complexes
US20100204466A1 (en) * 2005-12-14 2010-08-12 Abbott Laboratories One pot synthesis of tetrazole derivatives of rapamycin
US8129521B2 (en) 2005-12-14 2012-03-06 Abbott Laboratories One pot synthesis of tetrazole derivatives of rapamycin
US20100274035A1 (en) * 2005-12-20 2010-10-28 Mueller Patrik Process for Recycling Cyclopentadienyl Derivatives and Preparing Metallocenes From Recycled, Substituted Cyclopentadienyl Derivatives
US7951970B2 (en) 2005-12-20 2011-05-31 Basell Polyolefine Gmbh Process for recycling cyclopentadienyl derivatives and preparing metallocenes from recycled, substituted cyclopentadienyl derivatives
US12319772B2 (en) 2019-09-25 2025-06-03 Borealis Ag Catalysts
US12391774B2 (en) 2019-09-25 2025-08-19 Borealis Ag Heterophasic polypropylene copolymers

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